CN114835911B - Sorbitol type hyperbranched polyester, preparation method, application and polypropylene composite material - Google Patents
Sorbitol type hyperbranched polyester, preparation method, application and polypropylene composite material Download PDFInfo
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- CN114835911B CN114835911B CN202210545925.9A CN202210545925A CN114835911B CN 114835911 B CN114835911 B CN 114835911B CN 202210545925 A CN202210545925 A CN 202210545925A CN 114835911 B CN114835911 B CN 114835911B
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 74
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 74
- -1 polypropylene Polymers 0.000 title claims abstract description 71
- 229920006150 hyperbranched polyester Polymers 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 title claims abstract description 45
- 239000000600 sorbitol Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003365 glass fiber Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 13
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 229940087101 dibenzylidene sorbitol Drugs 0.000 claims description 6
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 5
- 229960002479 isosorbide Drugs 0.000 claims description 5
- CTPBWPYKMGMLGS-CIAFKFPVSA-N (3s,4s,5s,6r)-1,8-bis(4-methylphenyl)octa-1,7-diene-2,3,4,5,6,7-hexol Chemical compound C1=CC(C)=CC=C1C=C(O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=C(C)C=C1 CTPBWPYKMGMLGS-CIAFKFPVSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 125000006185 3,4-dimethyl benzyl group Chemical group [H]C1=C(C([H])=C(C(=C1[H])C([H])([H])[H])C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004135 Bone phosphate Substances 0.000 claims 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 239000000835 fiber Substances 0.000 abstract description 5
- 238000007667 floating Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 16
- 238000001746 injection moulding Methods 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229920000587 hyperbranched polymer Polymers 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 102100020871 Forkhead box protein G1 Human genes 0.000 description 2
- 101000931525 Homo sapiens Forkhead box protein G1 Proteins 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003562 lightweight material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012899 standard injection Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
Abstract
The invention relates to the technical field of polymer composite materials, in particular to sorbitol type hyperbranched polyester, a preparation method, application and a polypropylene composite material. The invention introduces the sorbitol structure into the branched end of the carboxyl-terminated hyperbranched polyester, so that the interfacial strength between the glass fiber and the polypropylene in the polypropylene composite material is effectively improved, the dispersion and the distribution of the glass fiber in the polypropylene are effectively improved, the surface smoothness of the composite material is improved, and the fiber floating phenomenon is effectively eliminated. Meanwhile, the composite material has no bad smell, so that the acceptance of the composite material in use is effectively improved. The composite material has good mechanical properties, in particular tensile strength and impact strength, can be applied to automobile light materials such as front end modules, engine covers, door inner plates and the like, and the fields of electronics, electrical appliances, household appliances and sports equipment, and has the advantages of simple process, high added value, suitability for industrial production and the like.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to sorbitol type hyperbranched polyester, a preparation method, application and a polypropylene composite material.
Background
Polypropylene (PP) is widely used because of its low density, good mechanical strength, heat resistance and chemical resistance. Glass Fiber (GF) has high strength and good rigidity, and is a reinforcing material commonly used in composite materials. GF reinforced PP is a composite material with excellent performance, has the characteristics of high strength, impact resistance, long-term fatigue, excellent creep performance and the like, is commonly used for replacing traditional reinforced engineering plastics and even steel materials, is widely applied to the fields of household electrical appliance manufacturing, automobile manufacturing and the like, and can realize the purpose of automobile weight reduction when applied to automobiles. However, because the compatibility between GF and PP is poor, the combination between GF and PP is weak, which is not beneficial to the improvement of the material performance, and therefore, the key point is to prepare a high-performance composite material, which is to improve the compatibility between GF and PP. At present, GF reinforced PP mainly comprises long glass fiber reinforced polypropylene and short glass fiber reinforced polypropylene.
The long glass fiber reinforced polypropylene has longer glass fiber length reserved in the product, so the product has better mechanical property. The Chinese patent 201610060142.6 prepares a long glass fiber reinforced polypropylene master batch by dipping in an extruder, sprays distilled water onto a matrix mixture to form a water-carrying material, and then mixes the long glass fiber reinforced polypropylene master batch with the water-carrying material to prepare a long glass fiber reinforced polypropylene foaming material. Chinese patent patents 201110008670.4, 201210025418.9 and 202111240362.4 utilize long glass fiber reinforced polypropylene master batch glass fiber reinforced polypropylene material. Chinese patent 201810397154.7 uniformly sprinkles halogen-free intumescent flame retardant on the surface of the polypropylene prepreg glass fiber felt, and then overlaps and stacks the polypropylene prepreg glass fiber felt for hot press molding to obtain the halogen-free intumescent flame retardant glass fiber reinforced polypropylene board.
In the prior art, the preparation process of the long glass fiber reinforced polypropylene is complex and has higher cost. Compared with long glass fiber reinforced polypropylene, the short glass fiber reinforced polypropylene product is processed by a standard injection molding machine, does not need complex glass fiber infiltration process and additional equipment, but has poor compatibility and dispersibility of the short glass fiber and polypropylene and limited application range. Therefore, there is a need to develop a short glass fiber reinforced polypropylene having a simple process and performance close to or superior to that of a long glass fiber reinforced polypropylene, and to be applied to lightweight materials for automobiles such as front and rear fenders, dashboards, automobile air inlet devices, fan brackets, air filter brackets, and cooling system parts.
Disclosure of Invention
The invention aims to solve the technical problem of providing sorbitol type hyperbranched polyester, a preparation method, application and a polypropylene composite material.
The technical scheme for solving the technical problems is as follows:
the invention provides sorbitol type hyperbranched polyester, which has a structural formula shown in a general formula (1):
wherein R ', R ' and R ' are the same or different and are respectively and independently represented as a structure of a general formula (2), a general formula (3) or a general formula (4):
wherein at least one X is represented by R 3 The remaining X's are denoted as H;
R 1 expressed as one of the general formula (5) or the general formula (6), wherein the position of the connection to-COOX is expressed as:
R 2 represented by one of the general formula (7) or the general formula (8), wherein the symbols are represented by the formula and R 1 The position of the connection:
R 3 represented by one of the general formula (9), the general formula (10) or the general formula (11):
further, the chemical structural formula isWherein R is 4 Is->R 5 Is->R 6 Is that
The invention provides a preparation method of sorbitol type hyperbranched polyester, which comprises the following steps:
firstly, uniformly mixing bio-base dihydric alcohol, triacid and an esterification catalyst, and reacting for 1-4 hours at 150-180 ℃ to synthesize carboxyl-terminated hyperbranched polyester, wherein the molar ratio of the bio-base dihydric alcohol to the triacid is (0.75-0.98): 1;
then the carboxyl-terminated hyperbranched polyester, sorbitol monomer, organic solvent and esterification catalyst react for 4 to 6 hours at the temperature of 100 to 120 ℃ to synthesize sorbitol-terminated hyperbranched polyester; wherein the molar ratio of the sorbitol monomer to the carboxyl of the carboxyl-terminated hyperbranched polyester is 1 (0.1-1), the mass of the esterification catalyst in the step is 0.5-1wt% of the carboxyl-terminated hyperbranched polyester, the mass ratio of the organic solvent to the carboxyl-terminated hyperbranched polyester is (1-3): 1, and the mass ratio of the water-carrying agent to the carboxyl-terminated hyperbranched polyester is (0.2-1): 1.
Further, the bio-based dihydric alcohol is one of 2, 5-furandimethanol or isosorbide, and the triacid is trimellitic anhydride;
the esterification catalyst is one of n-butyl titanate, ethyl propyl titanate, p-toluenesulfonic acid or phosphoric acid.
The sorbitol monomer is one of dibenzylidene sorbitol, di (p-methylbenzylidene) sorbitol or di (3, 4-dimethylbenzyl) sorbitol; the organic solvent is one of 1-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide or dioxane;
the water-carrying agent is one of toluene or dimethylbenzene.
The invention provides an application of sorbitol type hyperbranched polyester in a polypropylene composite material.
The invention provides a polypropylene composite material, wherein the components of the polypropylene composite material contain sorbitol type hyperbranched polyester.
Further, polypropylene resin and glass fiber are included.
Further, the mass percentage of the polypropylene resin is 40-90%, the mass percentage of the glass fiber is 10-60%, and the mass percentage of the sorbitol type hyperbranched polyester is 0.1% -1%.
Further, the glass fiber is one of alkali-free glass fiber, medium alkali glass fiber, high alkali glass fiber, alkali-resistant glass fiber or high-strength glass fiber.
The invention provides a preparation method of the polypropylene composite material, which comprises the following steps:
the polypropylene resin and the sorbitol type hyperbranched polyester are uniformly mixed, added into an extruder, then added with glass fiber, extruded and granulated to obtain the polypropylene composite material.
The invention has the beneficial effects that:
(1) The sorbitol type hyperbranched polyester can effectively improve the interfacial strength between glass fibers and polypropylene in the polypropylene composite material, effectively improve the dispersion and distribution of the glass fibers in the polypropylene, improve the surface smoothness of the composite material and effectively eliminate the fiber floating phenomenon.
(2) Compared with other sorbitol nucleating agents, the sorbitol hyperbranched polyester disclosed by the invention has no bad smell, so that the acceptance of the composite material in use is effectively improved.
(3) The sorbitol type hyperbranched polyester disclosed by the invention has the advantages that the topological structure of the hyperbranched polymer can effectively reduce the melting point, and the processability and the compatibility are improved.
(4) The added sorbitol type hyperbranched polyester can obviously improve the mechanical properties of polypropylene, in particular the tensile strength and the impact strength, and can be applied to the fields of automobile lightweight materials such as front end modules, engine covers, door inner plates and the like, electronics, electrical appliances and sports equipment.
(5) The polypropylene composite material has the advantages of simple process, high added value, suitability for industrial production and the like.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
The structural formula of the sorbitol type hyperbranched polyester is shown as a general formula (1):
wherein R ', R ' and R ' are the same or different and are respectively and independently represented as a structure of a general formula (2), a general formula (3) or a general formula (4):
wherein at least one X is represented by R 3 The remaining X is denoted as H.
R 1 Expressed as one of the general formula (5) or the general formula (6), wherein the position of the connection to-COOX is expressed as:
R 2 represented by one of the general formula (7) or the general formula (8), wherein the symbols are represented by the formula and R 1 The position of the connection:
R 3 represented by one of the general formula (9), the general formula (10) or the general formula (11):
according to the sorbitol type hyperbranched polyester, the sorbitol structure is introduced to the branches of the carboxyl-terminated polyester, so that the interfacial strength between glass fibers and polypropylene in the polypropylene composite material containing the hyperbranched polyester is effectively improved, the dispersion and distribution of the glass fibers in the polypropylene are effectively improved, the surface smoothness of the composite material is improved, and the fiber floating phenomenon is effectively eliminated.
The preparation method of the sorbitol type hyperbranched polyester comprises the following steps: firstly, uniformly mixing bio-base dihydric alcohol, triacid and esterification catalyst, and reacting for 1-4h at 150-180 ℃ to synthesize the carboxyl-terminated hyperbranched polyester, wherein the molar ratio of the bio-base dihydric alcohol to the triacid is (0.75-0.98): 1.
Preferably, the structure of the resulting carboxyl-terminated hyperbranched polyester is as follows:
r in the above formula 1 And R is 2 As previously described.
Then reacting carboxyl-terminated hyperbranched polyester, sorbitol monomer, organic solvent and esterification catalyst for 4-6 hours at 100-120 ℃ to synthesize sorbitol-type hyperbranched polyester; wherein the molar ratio of sorbitol monomer to carboxyl of carboxyl-terminated hyperbranched polyester is 1 (0.1-1), the mass of the esterification catalyst in the step is 0.5-1wt% of the carboxyl-terminated hyperbranched polyester, the mass ratio of the organic solvent to the carboxyl-terminated hyperbranched polyester is (1-3): 1, and the mass ratio of the water-carrying agent to the carboxyl-terminated hyperbranched polyester is (0.2-1): 1.
By the reaction, H on partial carboxyl of the carboxyl-terminated hyperbranched polyester is substituted by R3 to obtain the compound shown in the chemical formulaSorbitol-type hyperbranched polyester of (a). Wherein R is 4 Is thatR 5 Is->R 6 Is that
The value of x is an integer between 0 and 23.
The preparation method of the invention synthesizes the carboxyl-terminated hyperbranched polymer firstly and introduces the sorbitol structure at the branching end, and has the advantages of simple method, high efficiency and low cost.
Preferably, the bio-based dihydric alcohol is one of 2, 5-furandimethanol or isosorbide, and the triacid is trimellitic anhydride; the esterification catalyst is one of n-butyl titanate, ethyl propyl titanate, p-toluenesulfonic acid or phosphoric acid.
Preferably, the sorbitol monomer is one of dibenzylidene sorbitol, di (p-methylbenzylidene) sorbitol or di (3, 4-dimethylbenzyl) sorbitol; the organic solvent is one of 1-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide or dioxane;
preferably, the water-carrying agent is one of toluene or xylene.
The sorbitol type hyperbranched polyester disclosed by the invention can be applied to polypropylene composite materials.
The polypropylene composite material contains the sorbitol type hyperbranched polyester and also comprises polypropylene resin and glass fiber.
Preferably, the mass percentage of the polypropylene resin is 40-90%, the mass percentage of the glass fiber is 10-60%, and the mass percentage of the sorbitol type hyperbranched polyester is 0.1-1%.
Preferably, the glass fiber is one of alkali-free glass fiber, medium alkali glass fiber, high alkali glass fiber, alkali-resistant glass fiber or high strength glass fiber.
The preparation method of the polypropylene composite material comprises the following steps:
the preparation method comprises the steps of uniformly mixing polypropylene resin and sorbitol type hyperbranched polyester, adding the mixture into an extruder through a charging hopper, adding glass fibers from a glass fiber port, extruding and granulating to obtain the sorbitol type hyperbranched polyester modified polypropylene composite material.
The following illustrates the beneficial effects of the above scheme by specific examples:
example 1
76.8g of 2, 5-furandimethanol and 153.6g of trimellitic anhydride) are uniformly mixed and reacted for 1h at 180 ℃ to obtain the carboxyl-terminated hyperbranched polyester HBF-1, wherein the acid value is 301.6mgKOH/g, and the GPC test molecular weight is 1106g/mol. 111.6g of HBF-1, 47.4g of dibenzylidene sorbitol, 200ml of N, N-dimethylformamide, 50ml of dimethylbenzene and 0.9g of p-toluenesulfonic acid are uniformly mixed and reacted for 4 hours at 120 ℃ to synthesize the sorbitol type hyperbranched polyester HDBS-1.
500.0g of polypropylene, 500.0g of high alkali glass fiber and 5.0g of HDBS-1 are mixed for 5 minutes, and then extrusion granulation is carried out by using a double screw extruder, wherein the temperature of the extruder is 170 ℃,180 ℃,185 ℃,180 ℃,175 ℃ and the screw rotating speed is 50r/min. The obtained pellets were then subjected to an injection molding machine to prepare standard bars for testing mechanical properties, the mechanical properties of the composite materials were tested using a universal tester and an impact tester, and the flowability of the composite materials was tested using a melt index tester, and the results are shown in table 1.
Example 2
115.2g of 2, 5-furandimethanol and 192.0g of trimellitic anhydride are uniformly mixed and reacted for 1h at 180 ℃ to obtain carboxyl-terminated hyperbranched polyester HBF-2, wherein the acid value is 229.9mgKOH/g, and the GPC test molecular weight is 2898g/mol. 146.4g of HBF-2, 138.9g of dibenzylidene sorbitol, 300ml of N, N-dimethylformamide, 60ml of dimethylbenzene and 1.1g of ethyl propyl titanate are uniformly mixed and reacted for 4 hours at 120 ℃ to synthesize the sorbitol type hyperbranched polyester HDBS-2.
500.0g of polypropylene, 500.0g of high alkali glass fiber and 7.0g of HDBS-2 are mixed for 5 minutes, and then extrusion granulation is carried out by using a double screw extruder, wherein the temperature of the extruder is 170 ℃,180 ℃,185 ℃,180 ℃,175 ℃ and the screw rotating speed is 50r/min. The obtained pellets were then subjected to an injection molding machine to prepare standard bars for testing mechanical properties, the mechanical properties of the composite materials were tested using a universal tester and an impact tester, and the flowability of the composite materials was tested using a melt index tester, and the results are shown in table 1.
Example 3
134.4g of 2, 5-furandimethanol and 211.2g of trimellitic anhydride are uniformly mixed and reacted for 3 hours at 160 ℃ to obtain carboxyl-terminated hyperbranched polyester HBF-3, wherein the acid value is 205.5mgKOH/g, and the GPC test molecular weight is 6645 g/mol. Then, 65.5g of HBF-3, 49.6g of dibenzylidene sorbitol, 200ml of dioxane, 80ml of toluene and 0.5g of n-butyl titanate are uniformly mixed and reacted for 5 hours at 110 ℃ to synthesize the sorbitol type hyperbranched polyester HDBS-3.
500.0g of polypropylene, 500.0g of high alkali glass fiber and 10.0g of HDBS-3 are mixed for 5 minutes, and then extrusion granulation is carried out by using a double screw extruder, wherein the temperature of the extruder is 170 ℃,180 ℃,185 ℃,180 ℃,175 ℃ and the screw rotating speed is 50r/min. The obtained pellets were then subjected to an injection molding machine to prepare standard bars for testing mechanical properties, the mechanical properties of the composite materials were tested using a universal tester and an impact tester, and the flowability of the composite materials was tested using a melt index tester, and the results are shown in table 1.
Example 4
115.2g of isosorbide and 192.0g of trimellitic anhydride are uniformly mixed and reacted for 4 hours at 150 ℃ to obtain carboxyl-terminated hyperbranched polyester HSDS-2, wherein the acid value is 217.9mgKOH/g, and the GPC test molecular weight is 3035g/mol. Then, 154.5g of HSDS-2, 185.2g of di (p-methylbenzylidene) sorbitol, 400ml of N, N-dimethylacetamide, 80ml of dimethylbenzene and 1.3g of phosphoric acid are uniformly mixed and reacted for 6 hours at 100 ℃ to synthesize the sorbitol type hyperbranched polyester HMS-3.
500.0g of polypropylene, 500.0g of high alkali glass fiber and 7.0g of HMDBS-3 are mixed for 5 minutes, and then extrusion granulation is carried out by a double screw extruder, wherein the temperature of the extruder is 170 ℃,180 ℃,185 ℃,180 ℃,175 ℃ and the screw rotating speed is 50r/min. The obtained pellets were then subjected to an injection molding machine to prepare standard bars for testing mechanical properties, the mechanical properties of the composite materials were tested using a universal tester and an impact tester, and the flowability of the composite materials was tested using a melt index tester, and the results are shown in table 1.
Example 5
153.3g of isosorbide and 211.2g of trimellitic anhydride are uniformly mixed and reacted for 1h at 180 ℃ to obtain carboxyl-terminated hyperbranched polyester HSDS-3, wherein the acid value is 194.3mgKOH/g, and the GPC test molecular weight is 6920g/mol. 69.3g of HSDS-3, 39.7g of di (3, 4-dimethylbenzyl) sorbitol, 200ml of 1-methyl-2-pyrrolidone, 50ml of xylene and 0.6g of p-toluenesulfonic acid are uniformly mixed and reacted for 4 hours at 120 ℃ to synthesize the sorbitol type hyperbranched polyester HDS-4.
500.0g of polypropylene, 500.0g of high alkali glass fiber and 7.0g of HDS-3 are mixed for 5 minutes, and then extrusion granulation is carried out by using a double screw extruder, wherein the temperature of the extruder is 170 ℃,180 ℃,185 ℃,180 ℃,175 ℃ and the screw rotating speed is 50r/min. The obtained pellets were then subjected to an injection molding machine to prepare standard bars for testing mechanical properties, the mechanical properties of the composite materials were tested using a universal tester and an impact tester, and the flowability of the composite materials was tested using a melt index tester, and the results are shown in table 1.
Example 6
500.0g of polypropylene and 500.0g of high alkali glass fiber are mixed for 5 minutes, and then extrusion granulation is carried out by a double screw extruder, wherein the temperature of the extruder is 170 ℃,180 ℃,185 ℃,180 ℃,175 ℃ and the screw rotating speed is 50r/min. The obtained pellets were then subjected to an injection molding machine to prepare standard bars for testing mechanical properties, the mechanical properties of the composite materials were tested using a universal tester and an impact tester, and the flowability of the composite materials was tested using a melt index tester, and the results are shown in table 1. Wherein the test rate of the tensile property test is 10mm/min; setting the lower span of a simply supported beam for bending performance test to be 64mm, testing the speed to be 2mm/min, setting the notch depth of the notch impact strength of the cantilever beam to be 2mm, and setting the impact load to be 2.75J; melt mass flow rate test set temperature 190℃and load 2.16kg.
Table 1 results of Performance test of Polypropylene composite materials of examples
As can be seen from the test results of Table 1, the composites of examples 1 to 5 of the present invention were significantly higher in tensile strength, flexural strength, unnotched impact strength, and melt index than the composites of example 6 without the addition of the hyperbranched polymer. The composites of examples 1 to 5 are described as having good mechanical properties, in particular tensile strength and impact resistance, while also having good flowability. It can be seen that the sorbitol type hyperbranched polyester provided by the invention can be used for well modifying polypropylene. .
In addition, the surface smoothness of examples 1 to 5 was significantly higher than that of example 6, and there was no macroscopic fiber floating phenomenon, whereas example 6 showed fiber floating phenomenon, as observed for the composite surfaces of examples 1 to 6, respectively.
Finally, the composites of examples 1 to 5 have no off-flavors and are useful.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The sorbitol type hyperbranched polyester is characterized by having a structural formula shown in a general formula (1):
wherein R ', R ' and R ' are the same or different and are respectively and independently represented as a structure of a general formula (2), a general formula (3) or a general formula (4):
wherein at least one X is represented by R 3 The remaining X's are denoted as H;
R 1 expressed as one of the general formula (5) or the general formula (6), wherein the position of the connection to-COOX is expressed as:R 2 represented by one of the general formula (7) or the general formula (8), wherein the symbols are represented by the formula and R 1 The position of the connection:
R 3 represented by one of the general formula (9), the general formula (10) or the general formula (11):
2. the sorbitol-type hyperbranched polyester as claimed in claim 1, wherein the chemical structural formula is:wherein R is 4 Is->R 5 Is thatR 6 Is that
The value of x is an integer between 0-23.
3. The method for preparing the sorbitol-type hyperbranched polyester according to any one of claims 1 or 2, comprising the following steps:
firstly, uniformly mixing bio-base dihydric alcohol, triacid and an esterification catalyst, and reacting for 1-4 hours at 150-180 ℃ to synthesize carboxyl-terminated hyperbranched polyester, wherein the molar ratio of the bio-base dihydric alcohol to the triacid is (0.75-0.98): 1; the mass of the esterification catalyst in the step is 0.5-1wt% of the total mass of the dihydric alcohol and the tribasic acid;
then reacting the carboxyl-terminated hyperbranched polyester, sorbitol monomer, organic solvent, water carrying agent and esterification catalyst for 4-6 hours at 100-120 ℃ to synthesize sorbitol-terminated hyperbranched polyester; wherein the molar ratio of the sorbitol monomer to the carboxyl of the carboxyl-terminated hyperbranched polyester is 1 (0.1-1), the mass of the esterification catalyst in the step is 0.5-1wt% of the carboxyl-terminated hyperbranched polyester, the mass ratio of the organic solvent to the carboxyl-terminated hyperbranched polyester is (1-3): 1, and the mass ratio of the water-carrying agent to the carboxyl-terminated hyperbranched polyester is (0.2-1): 1.
4. A process for preparing a sorbitol-type hyperbranched polyester as claimed in claim 3, wherein,
the bio-based dihydric alcohol is one of 2, 5-furandimethanol or isosorbide, and the triacid is trimellitic anhydride;
the esterification catalyst is one of n-butyl titanate, isopropyl titanate, p-toluenesulfonic acid or phosphoric acid;
the sorbitol monomer is one of dibenzylidene sorbitol, di (p-methylbenzylidene) sorbitol or di (3, 4-dimethylbenzyl) sorbitol; the organic solvent is one of 1-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide or dioxane;
the water-carrying agent is one of toluene or dimethylbenzene.
5. Use of a sorbitol-type hyperbranched polyester as claimed in any one of claims 1 or 2 in polypropylene composite materials.
6. A polypropylene composite material, characterized in that the components of the polypropylene composite material contain the sorbitol-type hyperbranched polyester according to any one of claims 1 or 2.
7. The polypropylene composite of claim 6, further comprising a polypropylene resin and glass fibers.
8. The polypropylene composite material according to claim 7, wherein the mass percentage of the polypropylene resin is 40-90%, the mass percentage of the glass fiber is 10-60%, and the mass percentage of the sorbitol-type hyperbranched polyester is 0.1-1%.
9. The polypropylene composite of claim 7, wherein the glass fiber is one of an alkali-free glass fiber, a medium alkali glass fiber, a high alkali glass fiber, an alkali-resistant glass fiber, or a high strength glass fiber.
10. A process for the preparation of a polypropylene composite as claimed in any one of claims 7 to 9, comprising the steps of:
the polypropylene resin and the sorbitol type hyperbranched polyester are uniformly mixed, added into an extruder, then added with glass fiber, extruded and granulated to obtain the polypropylene composite material.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6114458A (en) * | 1998-09-23 | 2000-09-05 | International Business Machines Corporation | Highly branched radial block copolymers |
| CN1298343A (en) * | 1998-04-23 | 2001-06-06 | 纳幕尔杜邦公司 | Isosorbide containing polyesters and methods for making same |
| WO2002066541A1 (en) * | 2001-02-16 | 2002-08-29 | Perstorp Specialty Chemicals Ab | Process for manufacture of a carboxy terminated dendritic polyester |
| CN103476824A (en) * | 2011-02-23 | 2013-12-25 | 科学与工业研究委员会 | Process for preparing hyperbranched polyestersfield |
| CN104311807A (en) * | 2014-10-15 | 2015-01-28 | 重庆理工大学 | Polyester film-forming agent and glass fiber soakage agent compound |
| CN104603206A (en) * | 2012-07-02 | 2015-05-06 | 道达尔销售服务公司 | Bituminous compositions comprising additives having improved thermoreversible properties |
| CN105732315A (en) * | 2016-02-03 | 2016-07-06 | 苏州亚培克生物科技有限公司 | Sorbitol derivatives and preparing method and application of DBS polyolefin nucleating agent synthesized with sorbitol derivatives |
| CN111662507A (en) * | 2020-06-30 | 2020-09-15 | 万华化学集团股份有限公司 | Polypropylene material with high weld mark strength and preparation method thereof |
| JP2021066150A (en) * | 2019-10-28 | 2021-04-30 | 新日本理化株式会社 | High rigidity polypropylene resin molding and method for producing the same |
| CN113930058A (en) * | 2021-10-29 | 2022-01-14 | 中国科学院长春应用化学研究所 | Low-temperature thermoplastic plate composition and preparation method thereof |
| CN114276615A (en) * | 2021-12-28 | 2022-04-05 | 武汉金发科技有限公司 | Coloring reinforced polypropylene composite material and preparation method and application thereof |
| CN114395216A (en) * | 2021-12-31 | 2022-04-26 | 中南民族大学 | Bio-based hyperbranched polymer epoxy resin and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6485819B2 (en) * | 2000-12-19 | 2002-11-26 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic copolyesters |
| US6673870B2 (en) * | 2002-05-13 | 2004-01-06 | The Procter & Gamble Company | Compositions of polyolefins and hyperbranched polymers with improved tensile properties |
| KR20110028696A (en) * | 2009-09-14 | 2011-03-22 | 에스케이케미칼주식회사 | Polyester resin copolymerized with isosorbide and 1,4- cyclohexane dimethanol and preparing method thereof |
-
2022
- 2022-05-18 CN CN202210545925.9A patent/CN114835911B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298343A (en) * | 1998-04-23 | 2001-06-06 | 纳幕尔杜邦公司 | Isosorbide containing polyesters and methods for making same |
| US6114458A (en) * | 1998-09-23 | 2000-09-05 | International Business Machines Corporation | Highly branched radial block copolymers |
| WO2002066541A1 (en) * | 2001-02-16 | 2002-08-29 | Perstorp Specialty Chemicals Ab | Process for manufacture of a carboxy terminated dendritic polyester |
| CN103476824A (en) * | 2011-02-23 | 2013-12-25 | 科学与工业研究委员会 | Process for preparing hyperbranched polyestersfield |
| CN104603206A (en) * | 2012-07-02 | 2015-05-06 | 道达尔销售服务公司 | Bituminous compositions comprising additives having improved thermoreversible properties |
| CN104311807A (en) * | 2014-10-15 | 2015-01-28 | 重庆理工大学 | Polyester film-forming agent and glass fiber soakage agent compound |
| CN105732315A (en) * | 2016-02-03 | 2016-07-06 | 苏州亚培克生物科技有限公司 | Sorbitol derivatives and preparing method and application of DBS polyolefin nucleating agent synthesized with sorbitol derivatives |
| JP2021066150A (en) * | 2019-10-28 | 2021-04-30 | 新日本理化株式会社 | High rigidity polypropylene resin molding and method for producing the same |
| CN111662507A (en) * | 2020-06-30 | 2020-09-15 | 万华化学集团股份有限公司 | Polypropylene material with high weld mark strength and preparation method thereof |
| CN113930058A (en) * | 2021-10-29 | 2022-01-14 | 中国科学院长春应用化学研究所 | Low-temperature thermoplastic plate composition and preparation method thereof |
| CN114276615A (en) * | 2021-12-28 | 2022-04-05 | 武汉金发科技有限公司 | Coloring reinforced polypropylene composite material and preparation method and application thereof |
| CN114395216A (en) * | 2021-12-31 | 2022-04-26 | 中南民族大学 | Bio-based hyperbranched polymer epoxy resin and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Aditi Saikia，等."Tough and biodegradable thermosets derived by blending of renewable resource based hyperbranched epoxy and hyperbranched polyester".《Polymer Degradation and Stability》.2018,第159卷第15-22页. * |
| 杨雪芹，等."硅胶接枝1,3-2,4-二（对甲基亚苄基） 山梨醇成核剂的制备".《研究与开发》.2018,第36卷(第36期),第38-42页. * |
| 梁叶云，等."超支化聚酯制备高玻纤含量的尼龙／玻纤复合材料".《功能材料》.2018,49(6),第06103-06106,06113页. * |
| 陈渭，等."超支化硼螯合树脂的制备及性能".《广州化工》.2021,第49卷(第49期),第41-43,127页. * |
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